US7947948B2 - Two-dimensional radial-ejection ion trap operable as a quadrupole mass filter - Google Patents
Two-dimensional radial-ejection ion trap operable as a quadrupole mass filter Download PDFInfo
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- US7947948B2 US7947948B2 US12/205,750 US20575008A US7947948B2 US 7947948 B2 US7947948 B2 US 7947948B2 US 20575008 A US20575008 A US 20575008A US 7947948 B2 US7947948 B2 US 7947948B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
- H01J49/4205—Device types
- H01J49/422—Two-dimensional RF ion traps
- H01J49/423—Two-dimensional RF ion traps with radial ejection
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
- H01J49/4205—Device types
- H01J49/421—Mass filters, i.e. deviating unwanted ions without trapping
- H01J49/4215—Quadrupole mass filters
Definitions
- the present invention relates generally to mass spectrometers, and more particularly to a two-dimensional radial-ejection ion trap mass analyzer.
- Two-dimensional radial-ejection ion traps have been described extensively in the literature (see, e.g., Schwartz et al., “A Two-Dimensional Quadrupole Ion Trap Mass Spectrometer”, J. Am. Soc. Mass Spectrometry, 13: 659-669 (2002)) and are widely used for mass spectrometric analysis of a variety of substances, including small molecules such as pharmaceutical agents and their metabolites, as well as large biomolecules such as peptides and proteins.
- such traps consist of four elongated electrodes, each electrode having a hyperbolic-shaped surface, arranged in two electrode pairs aligned with and opposed across the trap centerline.
- At least one of the electrodes of an electrode pair is adapted with an aperture (slot) extending through the thickness of the electrode in order to permit ejected ions to travel through the aperture to an adjacently located detector.
- Ions are radially confined within the ion trap interior by applying opposite phases of a radio-frequency (RF) trapping voltage to the electrode pairs, and may be axially confined by applying appropriate DC offsets to end sections or lenses located axially outward of the electrodes or central sections thereof.
- RF radio-frequency
- a dipole resonant excitation voltage is applied across the electrodes of the apertured electrode pair (often referred to as the X-electrodes because they are aligned with the X-axis of a Cartesian coordinate system, which is oriented such that X and Y are the radial axes of the trap and Z is the longitudinal axis extending along the trap centerline) while the amplitude of the RF trapping voltage is ramped.
- This causes the trapped ions to come into resonance with the applied excitation voltage in order of their mass-to-charge ratios (m/z's).
- the resonantly excited ions develop unstable trajectories and are ejected from the trap through the aperture(s) of the X-electrodes to the detectors, which generate signals representative of the number of ejected ions.
- the detector signals are conveyed to a data and control system for processing and generation of a mass spectrum.
- a drawback to this approach is that when RF voltages are applied to the electrodes in the normal manner (whereby electrodes of one electrode pair receive a voltage equal in amplitude and opposite in polarity to the electrodes of the other electrode pair), the resultant electric field is not balanced, causing the centerline of the device to exhibit a significant RF potential.
- ions are then introduced into the trap interior along the centerline, for a given RF amplitude the acceptance of the ions can be significantly m/z-dependent, which is an undesired behavior.
- ions in a misbalanced field can effectively oscillate with different frequencies in the X- and Y-dimensions, which eliminates the possibility of conducting phase-locked resonance experiments in both dimensions.
- the oscillation frequency shifts associated with a changing ion trajectory amplitude are in opposite directions for ion motion in the X and Y-dimensions.
- a two-dimensional radial-ejection ion trap is constructed from four elongated electrodes arranged about the trap centerline.
- Each of the electrodes has an inwardly directed hyperbolic surface defining a hyperbolic radius r 0 and a longitudinally extending aperture.
- the four electrodes are equally spaced from the centerline by a distance r, wherein r is greater than r 0 , such that both electrode pairs are stretched by equal amounts relative to the “normal” spacing.
- This balanced field significantly reduces the m/z dependence of the ion injection process and allows ions having a wide m/z range to be injected at the same RF amplitude.
- it allows ion injection to be performed at high RF amplitudes (corresponding to high values of the Mathieu parameter q) relative to injection into a conventional unbalanced field, which has advantages relating to space charge capacity, elimination of unwanted low m/z ions, and higher ion frequency dispersion (facilitating higher resolution isolation or ejection of ions during ion injection).
- a further advantage of an ion trap of the foregoing construction is that the RF field produced thereby does not possess a significant octopolar field component; instead, the principal higher order field component is dodecapolar or icosapolar, which has advantages including that any ion frequency shifting is the same in both radial (X and Y) dimensions. This permits, for example, phase-locked resonance excitation to be performed between the X and Y dimensions.
- an ion trap constructed in accordance with an embodiment of the invention is that its field is symmetrical and more closely approximates that of a conventional round-rod quadrupole mass filter.
- the ion trap (alternatively referred to as a multipole structure) may be configured to be selectably operable as a radial-ejection ion trap mass analyzer or (by removing the DC potential well and adding a resolving DC component to the applied RF voltage) as a quadrupole mass filter analyzer.
- a mass spectrometer having an ion source for generating ions from a sample, a set of ion optics for guiding the ions from the ion source, a multipole device comprising four apertured elongated electrodes having hyperbolic surfaces arranged around the centerline such that each electrode is spaced at a stretched distance r from the centerline, and a controller, coupled to the multipole device, for applying RF and DC voltages to the electrodes to selectively operate the multipole device as a quadrupole mass filter or a two-dimensional radial-ejection ion trap mass analyzer.
- One specific implementation of this embodiment includes a quadrupole mass filter and a collision cell located upstream in the ion path from the multipole device, so that the mass spectrometer is operable (by adjustment of the RF and DC voltages applied to the multipole device) as a triple quadrupole mass spectrometer or as a hybrid Q-trap mass spectrometer.
- FIG. 1 is a symbolic diagram of a mass spectrometer utilizing a two-dimensional radial-ejection ion trap constructed in accordance with an embodiment of the invention
- FIG. 2 is a perspective view of the two-dimensional radial-ejection ion trap employed in the mass spectrometer of FIG. 1 ;
- FIG. 3 is a lateral cross-sectional view of the two-dimensional radial-ejection ion trap taken through the central portion of FIG. 2 ;
- FIG. 4 is a symbolic view of a another mass spectrometer, which includes a multipole structure that is selectively operable as a two-dimensional radial-ejection ion trap or a quadrupole mass filter; and
- FIG. 5 is a symbolic view of a variation on the mass spectrometer depicted in FIG. 4 , wherein a quadrupole mass filter and a collision cell are placed upstream in the ion path from the multipole device, such that the mass spectrometer is selectively operable in triple quadrupole or Q-trap analysis modes.
- FIG. 1 depicts the components of a mass spectrometer 100 in which a two-dimensional radial-ejection ion trap mass analyzer may be implemented, in accordance with an embodiment of the present invention. It will be understood that certain features and configurations of mass spectrometer 100 are presented by way of illustrative examples, and should not be construed as limiting the ion trap mass analyzer to implementation in a specific environment.
- An ion source which may take the form of an electrospray ion source 105 , generates ions from an analyte material, for example the eluate from a liquid chromatograph (not depicted).
- ions are transported from ion source chamber 110 , which for an electrospray source will typically be held at or near atmospheric pressure, through several intermediate chambers 120 , 125 and 130 of successively lower pressure, to a vacuum chamber 135 in which ion trap 140 resides. Efficient transport of ions from ion source 105 to ion trap 140 is facilitated by a number of ion optic components, including quadrupole RF ion guides 145 and 150 , octopole RF ion guide 155 , skimmer 160 , and electrostatic lenses 165 and 170 .
- Ions may be transported between ion source chamber 110 and first intermediate chamber 120 through an ion transfer tube 175 that is heated to evaporate residual solvent and break up solvent-analyte clusters.
- Intermediate chambers 120 , 125 and 130 and vacuum chamber 135 are evacuated by a suitable arrangement of pumps to maintain the pressures therein at the desired values.
- intermediate chamber 120 communicates with a port of a mechanical pump (not depicted), and intermediate pressure chambers 125 and 130 and vacuum chamber 135 communicate with corresponding ports of a multistage, multiport turbomolecular pump (also not depicted).
- ion trap 140 is provided with axial trapping electrodes 180 and 185 (which may take the form of conventional plate lenses) positioned axially outward from the ion trap electrodes to assist in the generation of a potential well for axial confinement of ions, and also to effect controlled gating of ions into the interior volume of ion trap 140 .
- Ion trap 140 is additionally provided with at least one set of detectors 190 (which may comprise only a single detector) that generate(s) a signal representative of the abundance of ions ejected from the ion trap.
- a damping/collision gas inlet (not depicted), coupled to a source of an inert gas such as helium or argon, will typically be provided to controllably add a damping/collision gas to the interior of ion trap 140 in order to facilitate ion trapping, fragmentation and cooling.
- an inert gas such as helium or argon
- control and data system (not depicted in FIG. 1 ), which will typically consist of a combination of general-purpose and specialized processors, application-specific circuitry, and software and firmware instructions.
- the control and data system also provides data acquisition and post-acquisition data processing services.
- mass spectrometer 100 is depicted as being configured for an electrospray ion source, it should be noted that the ion trap 140 may be employed in connection with any number of pulsed or continuous ion sources (or combinations thereof), including without limitation a matrix assisted laser desorption/ionization (MALDI) source, an atmospheric pressure chemical ionization (APCI) source, an atmospheric pressure photo-ionization (APPI) source, an electron ionization (EI) source, or a chemical ionization (CI) ion source.
- MALDI matrix assisted laser desorption/ionization
- APCI atmospheric pressure chemical ionization
- APPI atmospheric pressure photo-ionization
- EI electron ionization
- CI chemical ionization
- FIG. 1 depicts an arrangement of ion transfer tube 175 , tube lens 195 and electrostatic skimmer 160 for transporting and focusing ions from source chamber 105 to the vacuum regions of mass spectrometer 100
- alternative embodiments may employ for this purpose a stacked ring ion guide of the type described in U.S. patent application Ser. No. 12/125,013 to Senko et al. (“Ion Transport Device and Modes of Operation Thereof”), the contents of which are incorporated herein by reference.
- FIG. 2 is a perspective view of ion trap 140 .
- Ion trap 140 includes four elongated electrodes 205 a,b,c,d arranged in mutually parallel relation about a centerline 210 .
- Each electrode 205 a,b,c,d has a truncated hyperbolic-shaped surface 210 a,b,c,d facing the interior volume of ion trap 140 .
- each electrode is segmented into a front end section 220 a,b,c,d , a central section 225 a,b,c,d , and a back end section 230 a,b,c,d , which are electrically insulated from each other to allow each segment to be maintained at a different DC potential.
- each electrode 205 a,b,c,d is adapted with an elongated aperture (slot) 235 a,b,c,d that extends through the full thickness of the electrode to allow ions to be ejected therethrough in a direction that is generally orthogonal to the central longitudinal axis of ion trap 140 .
- Slots 235 a,b,c,d are typically shaped such that they have a minimum width at electrode surface 210 a,b,c,d (to reduce field distortions) and open outwardly in the direction of ion ejection. Optimization of the slot geometry and dimensions to minimize field distortion and ion losses is discussed by Schwartz et al. in U.S. Pat. No. 6,797,950 (“Two-Dimensional Quadrupole Ion Trap Operated as a Mass Spectrometer”), the disclosure of which is incorporated herein by reference.
- Electrodes 205 ,a,b,c,d (or a portion thereof) are coupled to an RF trapping voltage source 240 , excitation voltage source 245 , and DC voltage source 250 , all of which communicate with and operate under the control of controller 255 , which forms part of the control and data system.
- RF trapping voltage source is configured to apply RF voltages of adjustable amplitude in a prescribed phase relationship to pairs of electrodes 205 a,b,c,d to generate a trapping field that radially confines ions within the interior of ion trap 140 .
- Excitation voltage source 245 applies an oscillatory excitation voltage of adjustable amplitude and frequency across at least one pair of opposed electrodes to create a dipolar excitation field that resonantly excites ions for the purposes of isolation of selected species, collision induced dissociation, and mass-sequential analytical scanning.
- the excitation and RF trapping voltage amplitudes may be temporally varied in accordance with calibrated relationships experimentally determined by known techniques, or by the technique described in the U.S. patent application by Philip M. Remes et al.
- DC voltage source is operable to apply DC potentials to electrodes 205 a,b,c,d or sections thereof to, for example, generate a potential well that axially confines ions within ion trap 140 .
- axial confinement is achieved by applying an oscillatory voltage across the electrode end sections or electrodes positioned axially outward of electrodes 205 a,b,c,d to generate an axial pseudo-potential well.
- This alternative configuration provides the capability of simultaneous axial confinement of ions of opposite polarities, which is useful for certain ion trap functions, such as electron transfer dissociation (ETD) in which positive analyte ions are reacted with negative reagent ions to yield product ions.
- ETD electron transfer dissociation
- FIG. 3 depicts a lateral cross section of ion trap 140 taken through a medial location within central sections 225 a,b,c,d of electrodes 205 a,b,c,d . Electrodes 205 a,b,c,d are arranged into first and second pairs of electrodes, with the electrodes of each pair being located equidistant from and opposed across centerline 305 .
- first and second pairs of electrodes are aligned with, respectively, the X- and Y-axes of a Cartesian coordinate system having its origin located at centerline 305 , the first and second pairs of electrodes are respectively referred to herein as the X-electrodes (numbered 310 ) and Y-electrodes (numbered 320 ).
- ion trap 140 is conventionally provided with at least one set of detectors 190 , positioned adjacent to X-electrodes 310 , which receive ions ejected through the apertures of X-electrodes 310 and responsively generate a signal representative of the number of ejected ions.
- each electrode 205 a,b,c,d is located at a distance r (often referred to as the radius of the inscribed circle) from centerline 305 . Because r is selected to be greater than the hyperbolic radius r 0 of the electrode surfaces (the hyperbolic radius r 0 corresponding to the spacing of electrodes from the device centerline that would produce, in the absence of slots 235 a,b,c,d and truncation of hyperbolic surfaces 210 a,b,c,d , a pure quadrupolar field), both the X-electrodes 310 and Y-electrodes 320 are considered to be stretched.
- the elimination of the centerline RF potential substantially reduces the m/z dependence of the ion injection process and enables injection of ions having a wide range of m/z's at the same RF trapping voltage amplitude.
- the balanced RF field allows ion injection to be conducted at relatively high trapping RF voltage amplitudes (and correspondingly high values of the Mathieu parameter q), which possesses advantages of higher space charge capacity, elimination of unwanted low m/z ions, and higher ion frequency dispersion (which facilitates higher-resolution mass selection during ion injection).
- each electrode 205 a,b,c,d is spaced from the centerline by a distance r equal to at least 1.01*r 0 , and preferably in the range of 1.07*r 0 to 1.2*r 0 .
- the RF field produced within ion trap 140 has a higher-order field component (alternatively referred to as a field distortion) that is primarily dodecapolar with a smaller icosapolar (20-pole) component.
- a two-dimensional electric potential ⁇ (x,y,t) may be expanded in multipoles ⁇ N (x,y) as follows:
- V(t) is the voltage applied between an electrode and ground
- a N is the dimensionless amplitude of the multipole ⁇ N (x,y).
- Conventional radial-ejection two-dimensional ion traps, as well as the axial-ejection round-rod two-dimensional ion traps and multipoles described by Soudakov et al. in U.S. Pat. No. 6,897,438 (“Geometry of Generating a Two-Dimensional Substantially Quadrupolar Field”) produce RF fields that exhibit a relatively high octopole amplitude A 4 ; Soudakov et al.
- octopole field component that has an amplitude A 4 in the range of 1-4% of the quadrupole field amplitude A 2 .
- the RF field generated by ion trap 140 theoretically has no octopole field component, amplitude A 4 , but a relatively large dodecapole amplitude A 6 and smaller icosapole A 10 amplitude respectively.
- the dodecapole field amplitude (and icosapole field) will depend on the degree of stretching of electrode pairs 310 and 320 .
- the electrodes will be positioned to produce a dodecapole field amplitude of at least 0.2%, and preferably between 0.5 and 0.9% of the quadrupole field amplitude, and an octopole field amplitude of less than 0.001% of the quadrupole field amplitude (which may arise from imprecision in the electrode symmetry).
- the stretch may be such that the dodecapole field is minimized (ideally to zero) while the icosapole (20-pole) field remains.
- ion trap electrodes are preferably formed with hyperbolic surfaces, other implementations may utilize electrodes having inwardly curved surfaces of different shapes, including “round rod” electrodes of generally cylindrical geometry.
- Electrodes of one opposed pair are adapted with apertures opening to the exterior of the ion trap.
- Each electrode of the other opposed pair e.g., Y-electrodes 320
- the recesses will typically have a length approximately equal to the length of the apertures.
- the cross-sectional geometry of the recesses is selected such that the recesses and apertures affect the RF field in substantially identical manners, i.e., the recesses produce field faults equivalent to those produced by the apertures.
- This embodiment may be favorable for applications where ions are to be ejected in only one dimension (e.g., the X-dimension).
- the balanced, symmetric RF field established within ion trap 140 as well as the presence of apertures in both electrode pairs 310 and 320 , enable the use of various techniques and modes of operation that are difficult or impossible to implement in conventional ion traps that have asymmetric trapping fields with a relatively high octopole field component.
- ions may be resonantly excited in both the X-dimension and Y-dimension, for the purpose of producing ion fragmentation or ejection, by applying oscillatory excitation voltages of identical frequency across X-electrodes 310 and Y-electrodes 320 (in a conventional ion trap, the excitation voltage is applied across a single electrode pair.)
- the excitation voltages are applied in a constant phase relationship of adjustable value.
- ions may be mass-sequentially ejected through the apertures of Y-electrodes in addition to the apertures of X-electrodes, and the ions ejected through the Y-electrodes may be detected by an second set of detectors (not depicted) located adjacent thereto.
- an second set of detectors not depicted
- simultaneous analytical scans may be performed at different mass ranges by applying resonant excitation voltages of different frequencies across the X-electrodes and Y-electrodes; for example, an excitation voltage of relatively low frequency may be applied across Y-electrodes 320 , resulting in the mass-sequential ejection through the Y-electrodes of ions in a range of fairly high m/z values (e.g., 2000-20,000) while an excitation voltage of fairly high frequency may be applied across X-electrodes 310 to effect mass-sequential ejection through the X-electrodes of ions in a range of fairly low m/z values (e.g., 200-2000).
- an excitation voltage of relatively low frequency may be applied across Y-electrodes 320 , resulting in the mass-sequential ejection through the Y-electrodes of ions in a range of fairly high m/z values (
- “artifact” peaks caused by the misassignment of m/z values to ions that are not ejected at the proper value of the Mathieu parameter q may be eliminated or substantially reduced by applying an excitation voltage across the Y-electrodes at reduced frequency relative to the excitation voltage applied across the X-electrodes (which places q y >q x ).
- ions that have “jumped” over the resonance point associated with ejection in the X-dimension do not reach the detectors located adjacent to X-electrodes 310 (which would result in the generation of an artifact peak), but are instead ejected in the Y-dimension through Y-electrodes 320 .
- ion trap 140 may constitute the sole mass analyzer of mass spectrometer 100 .
- ion trap 140 may be combined with one or more separate mass analyzers in a hybrid mass spectrometer architecture to enable serial or parallel analysis of sample ions.
- ion trap 140 may be combined with an Orbitrap analyzer utilizing the instrument architecture embodied in the LTQ Orbitrap mass spectrometer available from Thermo Fisher Scientific (San Jose, Calif.).
- ion trap 140 may be employed for both analytical scanning and for manipulation or processing of ion populations (e.g., isolation of ions within a prescribed range of m/z's and/or one or more stages of fragmentation) prior to conveyance of the resultant ions to a downstream mass analyzer for acquisition of a mass spectrum.
- ion trap 140 may be arranged adjacent to another two-dimensional ion trap maintained at a different pressure to form a dual-trap mass analyzer, as described in U.S. Patent Application Pub. No. 2008-0142705A1 for “Differential-Pressure Dual Ion Trap Mass Analyzer and Methods of Use Thereof” by Jae C.
- an ion optic is provided to transfer ions between the ion traps such that operations that are more favorably performed at relatively high pressures (e.g., ion cooling and fragmentation) are conducted within the high-pressure ion trap, and operations more favorably performed at relatively low pressures (e.g., m/z isolation and analytical scanning) are conducted within the low-pressure ion trap.
- relatively high pressures e.g., ion cooling and fragmentation
- relatively low pressures e.g., m/z isolation and analytical scanning
- ion trap 140 may be operated as a quadrupole mass filter (QMF) to provide m/z-filtering of a continuous or quasi-continuous ion beam.
- QMF quadrupole mass filter
- a conventional radial ejection ion trap, in which only two of the four electrodes are apertured, is generally not suitable for use as a QMF due to its X-Y asymmetry.
- Operation of ion trap 140 in QMF mode requires the inclusion of a filtering DC component in the RF voltages applied to electrodes 205 a,b,c,d , such that one electrode pair (e.g., X-electrode pair 310 ) receives a potential of +(U-V cos ⁇ t) and the other electrode pair (e.g., Y-electrode pair 320 ) receives a potential of ⁇ (U-V cos ⁇ t), where U is the filtering DC component, and V is the amplitude of the RF voltage.
- a filtering DC component in the RF voltages applied to electrodes 205 a,b,c,d , such that one electrode pair (e.g., X-electrode pair 310 ) receives a potential of +(U-V cos ⁇ t) and the other electrode pair (e.g., Y-electrode pair 320 ) receives a potential of ⁇ (U-V cos
- the m/z range of the transmitted ions is determined by the values of U and V, and ions having a desired range of m/z values may be selected for transmission by appropriately adjusting the values of U and V.
- ion trap 140 When operated in QMF mode, ion trap 140 may be “parked” by temporally fixing the values of U and V such that only a single ion species is transmitted, or may instead be “scanned” by progressively changing U and/or V such that the m/z of the transmitted ions varies in time.
- electrodes 205 a,b,c,d may be lengthened relative to a standard two-dimensional ion trap mass analyzer. Lengthening the electrodes would also provide increased ion storage capacity and hence improved sensitivity when operation in ion trap mode is desired.
- FIG. 4 depicts a mass spectrometer 400 utilizing an ion trap (referred to hereinafter as a multipole device) 140 that is selectively operable in QMF mode.
- the architecture of mass spectrometer 400 is closely similar to that of mass spectrometer 100 of FIG. 1 , with the addition of another detector 410 disposed axially outward of multipole device 140 .
- a filtering DC component is added to the RF voltage applied to the multipole device 140 electrodes by RF/DC voltage source 415 , in the manner known in the art and described above. Ions enter an inlet end of multipole device 140 as a continuous or quasi-continuous beam.
- Ions in the selected range of m/z values maintain stable trajectories within the interior of multipole device 140 and leave multipole device 140 via an outlet end thereof, and are thereafter delivered to detector 410 , which generates a signal representative of the abundance of transmitted ions. Ions having m/z values outside of the selected range develop unstable trajectories within multipole device 140 and hence do not arrive at detector 410 .
- DC offsets applied to electrodes 205 a,b,c,d and axial trapping electrodes 180 and 185 by DC voltage source 155 are set to enable the transport of the selected ions through multipole device 140 to detector 410 .
- the filtering DC component is removed, and suitable DC offsets are applied to the end sections of electrodes 205 a,b,c,d and/or to axial trapping electrodes 180 and 185 to establish a potential well that enables trapping of ions within the interior volume of multipole device 140 .
- the ions may then be subjected to one or more stages of isolation and fragmentation, if desired, and the ions or their products may be mass analyzed by resonantly ejecting the ions to detectors 190 , in accordance with known techniques.
- the frequency of the excitation voltage applied by excitation voltage source 250 during an analytical scan is equal to one-half or one-third of the frequency of the RF trapping voltage, and the phase of the excitation voltage is locked to the RF trapping voltage such that the phase relationship is maintained at a constant preselected value during the scan.
- the value of the Mathieu parameter q at which ions are ejected will depend on the ratio of the frequencies of the excitation and RF trapping voltages. So as to provide extended mass operation, i.e., the ability to detect ions over a larger range of m/z's, the excitation voltage frequency may be set to a relatively small integer fraction, e.g.
- a damping/collision gas may be added to the interior of multipole device 140 during its operation in ion trap mode.
- the damping/collision gas may be pumped away such that the interior volume is maintained at a low pressure conducive to good filtering performance.
- multipole device 140 may be automatically switched between ion trap and QMF modes in a data-dependent manner, whereby the acquisition of mass spectral data that satisfies specified criteria triggers mode switching.
- multipole device 140 may initially be operated in QMF mode to provide single ion monitoring (SIM) of an ion species of interest.
- SIM single ion monitoring
- detector 410 When detector 410 generates a signal indicative of the presence of the ion species of interest, multipole device 140 may be automatically switched to operation in ion trap mode in order to perform MS/MS or MS n analysis for confirmation of the identification of the ion species of interest or to provide structural elucidation.
- FIG. 5 depicts another mass spectrometer 500 , in which multipole device 140 is placed downstream of a quadrupole mass filter (QMF) 510 and a collision cell 520 .
- QMF 510 may take the form of a conventional multipole structure operable to selectively transmit ions within an m/z range determined by the applied RF and DC voltages.
- Collision cell 520 may also be constructed as a conventional multipole structure to which an RF voltage is applied to provide radial confinement.
- the interior of collision cell 520 is pressurized with a suitable collision gas, and the kinetic energies of ions entering collision cell 520 may be regulated by adjusting DC offset voltages applied to QMF 510 , collision cell 520 and lens 530 .
- multipole device 140 is selectably operable in an ion trap mode or a QMF mode and may be switched between the modes by adjusting or removing the RF, filtering DC, and DC offset voltages applied to electrodes 205 a,b,c,d and axial trapping electrodes 180 and 185 , and by adding or removing collision/damping gas to or from the interior volume.
- mass spectrometer 500 When multipole device 140 is operated in QMF mode, mass spectrometer 500 functions as a conventional triple quadrupole mass spectrometer, wherein ions are selectively transmitted by QMF 510 , fragmented in collision cell 520 , and the resultant product ions are selectively transmitted by multipole device 140 to detector 540 .
- Samples may be analyzed using standard techniques employed in triple quadrupole mass spectrometry, such as precursor ion scanning, product ion scanning, single- or multiple reaction monitoring, and neutral loss monitoring, by applying (either in a fixed or temporally scanned manner) appropriately tuned RF and DC voltages to QMF 510 and multipole device 140 .
- Switching multipole device 140 to ion trap mode causes mass spectrometer 500 to function as a QMF-ion trap instrument (commonly referred to in the art as a “Q-trap”). Ions are selectively transmitted through QMF 510 and undergo collision induced dissociation in collision cell 520 .
- the resultant product ions are delivered to multipole device 140 for trapping, manipulation and mass analysis.
- the product ions delivered to multipole device 140 may be subjected to one or more additional stages of fragmentation in order to provide confirmation of the identification of an ion species of interest.
- acquisition of a mass spectrum may be performed by resonantly ejecting the ions to detectors 190 in accordance with known techniques.
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Abstract
Description
x 2 −y 2 =r 0 2
for the
x 2 −y 2 =−r 0 2
for the Y-
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Application Number | Priority Date | Filing Date | Title |
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US12/205,750 US7947948B2 (en) | 2008-09-05 | 2008-09-05 | Two-dimensional radial-ejection ion trap operable as a quadrupole mass filter |
EP09792190A EP2356669A2 (en) | 2008-09-05 | 2009-09-02 | Two-dimensonal radial-ejection trap operable as a quadrupole mass filter |
JP2011526174A JP5667569B2 (en) | 2008-09-05 | 2009-09-02 | Two-dimensional radially emitted ion trap that can operate as a quadrupole mass filter |
PCT/US2009/055777 WO2010028081A2 (en) | 2008-09-05 | 2009-09-02 | Two-dimensonal radial-ejection trap operable as a quadrupole mass filter |
CA2736120A CA2736120C (en) | 2008-09-05 | 2009-09-02 | Two-dimensional radial-ejection ion trap operable as a quadrupole mass filter |
CN200980133968.9A CN102138196B (en) | 2008-09-05 | 2009-09-02 | Two-dimensonal radial-ejection trap operable as a quadrupole mass filter |
US13/085,696 US8415617B2 (en) | 2008-09-05 | 2011-04-13 | Two-dimensional radial-ejection ion trap operable as a quadrupole mass filter |
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Also Published As
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CA2736120A1 (en) | 2010-03-11 |
US20100059670A1 (en) | 2010-03-11 |
US20110186733A1 (en) | 2011-08-04 |
EP2356669A2 (en) | 2011-08-17 |
CN102138196B (en) | 2014-07-02 |
JP2012502433A (en) | 2012-01-26 |
CA2736120C (en) | 2014-06-03 |
US8415617B2 (en) | 2013-04-09 |
JP5667569B2 (en) | 2015-02-12 |
WO2010028081A2 (en) | 2010-03-11 |
CN102138196A (en) | 2011-07-27 |
WO2010028081A3 (en) | 2010-04-22 |
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